US10926513B2 - Gradient nanoparticle-carbon allotrope-polymer composite material - Google Patents

Gradient nanoparticle-carbon allotrope-polymer composite material Download PDF

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US10926513B2
US10926513B2 US13/880,270 US201113880270A US10926513B2 US 10926513 B2 US10926513 B2 US 10926513B2 US 201113880270 A US201113880270 A US 201113880270A US 10926513 B2 US10926513 B2 US 10926513B2
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US20130273273A1 (en
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Zachary R. Greenhill
Joseph J. Belbruno
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Greenhill Antiballistics Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/30—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being formed of particles, e.g. chips, granules, powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/048—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
    • F16F7/00—Vibration-dampers; Shock-absorbers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/04—Protection helmets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00—Personal protection gear
    • F41H1/04—Protection helmets
    • F41H1/08—Protection helmets of plastics; Plastic head-shields
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H7/00—Armoured or armed vehicles
    • F41H7/02—Land vehicles with enclosing armour, e.g. tanks
    • F41H7/04—Armour construction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42D—BLASTING
    • F42D5/00—Safety arrangements
    • F42D5/04—Rendering explosive charges harmless, e.g. destroying ammunition; Rendering detonation of explosive charges harmless
    • F42D5/045—Detonation-wave absorbing or damping means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0228—Vinyl resin particles, e.g. polyvinyl acetate, polyvinyl alcohol polymers or ethylene-vinyl acetate copolymers
    • B32B2264/0235—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
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    • B32B2437/00—Clothing
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    • B32B2571/00—Protective equipment
    • B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to protective materials and, more specifically, to a material that diminishes the effect of a shock wave.
  • Material designs for handling the impact of an external stimulus include, for example, woven fabrics, ceramic materials, and composite systems. Kevlar®, Zylon®, Armos®, Spectra® are commercially available fabrics made from high-strength fibers. Another material is ballistic steel, which is comprised of hardened high tensile steel, woven into fiber form. Further, boron carbide can be used as a material, for example, in the production of body armor.
  • Ceramic materials in particular ceramic metal composites have found utility in light weight body armor.
  • a shock wave attenuating material that includes a substrate layer.
  • a plurality of shock attenuating layers is disposed on the substrate layer.
  • Each of the plurality of shock attenuating layers includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter and a graphitic layer disposed adjacent to the gradient nanoparticle layer.
  • the graphitic layer includes a plurality of carbon allotrope members suspended in a matrix.
  • the invention is a helmet that includes a helmet member configured to be worn by a user.
  • a plurality of shock attenuating layers is applied to the helmet member.
  • Each shock attenuating layer includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter; and a graphitic layer disposed adjacent to the gradient nanoparticle layer, the graphitic layer including a plurality of carbon allotrope members suspended in a matrix.
  • the invention is an armor unit that includes a structural element, an armor plate and a plurality of shock attenuating layers.
  • the plurality of shock attenuating layers is disposed in a predetermined relationship with at least one of the structural element and the armor plate.
  • Each shock attenuating layer includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter; and a graphitic layer disposed adjacent to the gradient nanoparticle layer, the graphitic layer including a plurality of carbon allotrope members suspended in a matrix.
  • the invention is a personal body armor unit that includes a ceramic plate, a high mass member and a nanoparticle shock wave attenuating material layer.
  • the high mass member is disposed adjacent to the ceramic plate.
  • the nanoparticle shock wave attenuating material layer is disposed on the high mass member.
  • the nanoparticle shock wave attenuating material layer can be disposed between the high mass member and the ceramic plate. Similarly, the nanoparticle shock wave attenuating material layer can be disposed outside of the high mass member or the ceramic plate or both. It is understood that any combination of these configurations fall within the scope of the invention.
  • FIG. 1 is a schematic diagram of one embodiment of a shock wave attenuating material.
  • FIG. 2A is a schematic diagram of one embodiment of a gradient nanoparticle layer.
  • FIG. 2B is a schematic diagram of one embodiment of a graphitic layer.
  • FIG. 3 is a schematic diagram of the embodiment shown in FIG. 1 , demonstrating shock wave attenuation.
  • FIG. 4 is a schematic diagram of one embodiment of a helmet.
  • FIG. 5 is a schematic diagram of one embodiment of an armor unit.
  • FIG. 6 is a schematic diagram of one embodiment of a body armor unit.
  • FIG. 7 is a schematic diagram of one embodiment of a body armor unit.
  • FIG. 8 is a schematic diagram of one embodiment of a body armor unit.
  • a shock wave attenuating material 100 includes a substrate layer 104 and a plurality 110 of shock attenuating layers disposed on the substrate layer.
  • Each of the plurality 110 of shock attenuating layers includes a gradient nanoparticle layer 114 and a graphitic layer 118 disposed adjacent to the gradient nanoparticle layer 114 .
  • the shock wave attenuating material 100 would include at least 10 gradient nanoparticle layers 114 alternating with at least 10 graphitic layers 118 (while only three are shown in FIG. 1 for the sake of simplicity).
  • each nanoparticle layer 114 includes a plurality of nanoparticles 120 of different diameters (at least two different diameters) that are arranged in a gradient from smallest diameter to largest diameter.
  • the specific orientation of the gradient depends on the specific application for which the material is being used.
  • the graphitic layer 118 includes a plurality of carbon allotrope members 128 suspended in a matrix 124 .
  • the carbon allotrope members 128 can include graphene sheets, carbon nanotubes, fullerenes, functionalized graphene sheets, functionalized carbon nanotubes, and functionalized fullerenes.
  • the nature of the substrate may be varied.
  • Two potential substrates are polycarbonate and carbon fiber composites/laminates.
  • a thicker (yet still transparent) polymer-graphene composite layer may be employed directly as the substrate.
  • the gradient structure may be any of those shown, for example, in U.S. Patent Publication No. US-2011-0212320-A1, which is incorporated herein by reference, as well as others built up from the same principles.
  • One embodiment of a gradient structure has a total thicknesses of the order of 5-10 ⁇ m, which can then be repeated as many times as required.
  • a fullerene layer may be directly deposited by coating, from a toluene solution, onto the gradient structure in thicknesses as small as a monolayer.
  • nanotubes and graphene or graphene oxide sheets may be coated from suspensions in organic solvents such as chloroform.
  • these two allotropes may also be (preferentially) deposited as polymer composites.
  • the use of a polymer composite provides additional structural integrity to the overall coating and, more importantly, provides additional impact regions for the generation of partially reflected shock waves and will further reduce the overall passage of the shock energy from the impact site to the protection site.
  • Carbon allotrope members 128 can be functionalized as a graphene oxide.
  • nanotubes and fullerenes can be functionalized with carboxylic acid, amines, can be hydroxylated or carboxylated.
  • the graphitic layers 118 are of a thickness that is sufficient to reflect at least a portion of a shock wave impinging thereon.
  • the thickness of the graphitic layers 118 will depend on the type of shock wave that the designer desires to protect against.
  • the first gradient nanoparticle layer 114 begins to attenuate the shock wave 304 and the first graphitic layer 118 reflects a portion of the shock wave 306 , thereby generating destructive interference with any residual shock wave energy.
  • Successive waves 308 and 312 reflect in a similar fashion to generate reflected waves 310 and 314 , which further interfere with residual shock energy.
  • the carbon or carbon composite layers mark the end of one nanostructure and the start of the next.
  • a significant reduction of the incident shock wave occurs after passage through less than 10 ⁇ m of gradient nanoparticles.
  • Stacks or layers of such structures with the carbon and/or carbon composites are interspersed and define the layer or stack limit. The effect, at each carbon interface, will be to create a backward traveling wave causing attenuation of the incident shock wave, as well as a much reduced forward transmitted shock wave, which passes in to the next layer of the structure.
  • a stack of 50 alternating gradient nanoparticle structures (each composed of 30 nanoparticle layers) and composite layers would result in a 1 mm thick coating and significant attenuation of the incident shock wave.
  • Each of these 50 gradient or composite layers is one-fifth the thickness of the typical human hair.
  • the shock wave attenuating material 110 can be part of a helmet 400 or helmet liner.
  • a helmet 400 includes a helmet member 402 configured to be worn by a user, such as an Enhanced Combat Helmet [ECH] used in military applications.
  • the helmet member 402 could be made from a para-aramid synthetic fiber composite, such as Kevlar®.
  • the helmet could be of the type used in sports.
  • the shock wave attenuating material 110 could be used in a baseball helmet, a football helmet, a hockey helmet, a bicycling helmet, or the like.
  • the helmet 400 could include an outer shell (such as, e.g., acrylonitrile butadiene styrene), a shock wave attenuating material 110 layer and an inner shell.
  • the helmet 400 could even include an outer shell and several layers of shock wave attenuating material 110 alternating with high mass material layers.
  • the high mass material could include, for example, a high density plastic, a composite, fiber glass, a para-aramid synthetic fiber composite, a vinyl, acrylonitrile butadiene styrene, an acrylic, a metal, or any other material typically used in a helmet.
  • a shock-absorbing foam liner may also be added to the helmet.
  • the shock wave attenuating material 110 can be part of a an armor unit 500 , which can include a structural element 502 , such as a vehicle panel.
  • An outer armor plate 510 such as a ceramic or composite plate, provides an outer armor surface.
  • the shock wave attenuating material 110 is disposed between the structural element 502 and the armor plate 510 .
  • the shock wave attenuating material 110 could also be outside of either the structural element 502 or the armor plate 510 or both. It will be appreciated that any combination of these configurations will fall within the scope of the invention.
  • a body armor assemblage 600 such as an interceptor body armor assemblage (of the type used in the Improved Outer Tactical Vest, Improved Modular Tactical Vest and the US Army and USMC plate carriers).
  • Such an assemblage 600 would include an armor plate 602 (such as a ceramic plate) with a high mass member.
  • materials suitable for use in the high mass member include: a high density polymer 610 (such as an ultra high molecular weight polyethylene), a para-aramid synthetic fiber composite, a carbon fiber composite, a metal, a ceramic and combinations thereof.
  • the shock wave attenuating material 110 can be applied to the high density polymer 610 on the high density polymer 610 opposite from the armor plate 602 on the side adjacent to the body of the user. This latter application helps solve the problem of backface deformation. As shown in FIG. 7 , in one embodiment of a personal body armor assemblage 620 , the shock wave attenuating material 110 is disposed between the high density polymer 610 and the armor plate 602 . As shown in FIG. 8 , multiple layers of shock wave attenuating material 110 may be applied to the armor assemblage 630 .
  • the shock wave attenuating material 110 can be applied to such devices as soccer shin guards, baseball catchers' chest pads, football shoulder pads, baseball mitts and the like. In can also be applied to such devices as golf clubs and baseball bats to reduce the effects of shock associated with their use.
  • the gradient nanoparticle composite material is capable of absorbing an impact of a shock wave that, for example, is produced by an explosion or caused during operation of a device. In some embodiments, the gradient nanoparticle composite material is capable of mitigating and/or remediating one or more secondary blast effects resulting from the explosion.
  • the gradient nanoparticle composite material is capable of reacting to and/or interacting with one or more stimuli existing in a blast zone environment.
  • the material can absorb at least a portion of an initial blast impact and/or the over pressure wave resulting from an explosion.
  • gradient nanoparticle composite material can be designed to mitigate and/or remediate one or more related blast effects resulting from the blast impact itself.
  • some embodiments can provide a composite material that through intelligent design of the system can not only reduce blast impact with greater efficiency and efficacy, but that can also mitigate and/or remediate one or more secondary blast effects.
  • the gradient nanoparticle composite material can provide bomb blast mitigation and/or remediation by reducing the reflective value of the bomb blast by absorption of the bomb blast energy.
  • the primary mitigating and/or remediating process can be by absorption of the bomb blast shock wave.
  • the mitigating and/or remediating process can be by absorption of the pre-over pressure wave that precedes the shock wave. Absorption of the shock wave and/or the pre-over pressure wave can occur through one or more mechanisms, including, for example, momentum transfer, destruction of the spatial symmetry of, e.g., the blast wave, plastic deformation, rupture of particles, e.g. filled and unfilled core-shell particles, restitution, and interparticle/interlayer shear.
  • the gradient nanoparticle composite material can provide a platform from which a wide variety of blast effects can be mitigated and/or remediated.
  • the absorbed energy can be utilized to rupture, e.g., microcapsules to introduce a series or selection of materials or material systems into the blast environment and to thus mitigate and/or remediate the blast effects.
  • the gradient nanoparticle composite material can provide a relatively light weight material that can be applied to preexisting structures or systems with no deleterious effects on the performance attributes of the pre-existing structure or system.
  • Some embodiments provide bomb proofing, impact or smart material applications.
  • bomb proof applications include receptacles and liners (such as in waste receptacles and bags etc.), satellites, helicopters, and high tech devices (computer/hardware casings, cable protection), construction (buildings and their facades), bridges and their structural members, pipes and pipelines (for fossil fuels, conduits, utilities), automotive (door panels, bumpers, dashboards, windshields and windows, undercarriages and roofs), aerospace (interior/exterior of planes), etc.
  • the gradient nanoparticle composite material can be used in connection with military equipment, structures, vehicles, vessels and crafts for land, sea, and airborne forces to include armored and unarmored vehicles, aircraft, (which includes helicopters and unmanned drones), and nautical vessels such as submarines, ships, boats and the like.
  • the gradient nanoparticle composite material can be applied as an exterior coating, film, intermediate layer and/or as a panel to pre-existing equipment or, alternatively, can be utilized for forming structural components of the military vehicle, aircraft, or nautical vessel.
  • the application of gradient nanostructured composites for the attenuation of shock waves is based on the same principles that apply macroscopic granular spheres to create blast walls.
  • Granular materials, especially arranged in a gradient create mismatching of the solitary wave at each particle contact point and, hence, attenuation of that wave.
  • the effect is a combination of passive and active physical processes: absorption, distortion, and engineered redirection of the shock wave without appreciable heating.
  • the composite causes destructive interference of the shock wave to attenuate the incident wave.
  • the composite an ordered structure including selected solid, hollow and filled nanoparticles, may be coated onto a surface (e.g., a protective device, such as a helmet) and may also be produced as a self-supported liner (using plastic containment). Additionally, while the gradient array provides shock attenuation, the material within the filled nanoparticles acts to create an indicator that the user has experienced a shock wave sufficient to cause mild or severe traumatic brain injury while wearing the protective device, such as a helmet.
  • the final product is a lightweight coating that does not change the flexibility of the treated material and which can be made transparent by careful choice of nanoparticle materials.
  • the protective device may be recoated, if that technology was used in production, or the liner may be replaced, if that approach was employed.
  • KE OUT KE IN ⁇ [ 2 ⁇ ( 1 - q ) 3 - E L ] 2 ( 1 - q ) 3 ⁇ [ 1 + ( 1 - q ) 3 ] 2 ⁇ N - 1 ( 1 )
  • nanospheres may be solid and made of any number of polymers, metals, ceramics or other materials, so that the elastic properties and the interparticle forces may be varied. Hollow nanoparticles offer an interesting capability to insert voids, spheres shattered under compression by the shock wave, which would only act when the particles are compressed by sufficient force.
  • Polymer nanoparticle shells may be constructed to carry other materials within the nanoparticle, providing the means to include in the structure indicators of the passage of a blast wave or the ability to release a beneficial agent to the users upon activation by the blast wave.
  • the final product is a lightweight coating that does not change the flexibility of the treated material and can be made transparent by careful choice of nanoparticle materials. Taken as a whole, these characteristics of nanostructured gradient arrays provide a menu for the development of blast wave protection with targeted applications.
  • One version involves a structure that incorporates carbon allotrope (fullerene, nanotubes or graphene) and/or carbon allotrope-polymer composite layers into the overall structure.
  • the carbon allotropes provide increased strength to the nanostructure since these materials rank among the strongest known.
  • One embodiment employs “stacks” or “layers” of such structures with the carbon and/or carbon composites interspersed and defining the layer or stack limit. The effect, at each carbon interface, is to create a backward traveling wave causing attenuation of the incident shock wave, as well as a greatly reduced forward transmitted shock wave, which passes in to the next layer of the structure.
  • a stack of 50 gradient nanoparticle structures (each composed of 30 nanoparticle layers) and composite layers would result in a 1 mm thick coating and significant attenuation of the incident shock wave.
  • This structure would have a thickness of approximately 100 ⁇ m or 10 human hairs.
  • samples were made using a spin coating technique and measuring approximately 6 cm 2 .
  • Samples having a wide variety of gradients and employed solid polymer, solid silica, hollow polymer and filled (with long-chain hydrocarbons, as prototypes) silica nanoparticles were employed.
  • Mono-dispersed coatings, tapered gradients (large to small and small to large) and repetitive gradients using polycarbonate substrates treated with UV light to make the surface polar were also used.
  • Most samples employed a hexagonal close packed of the nanoparticles.
  • the coatings typically had a tapered gradient of 320 nm/260 nm/220 nm/160 nm/130 nm.
  • the following table shows experimental impact shock results for polystyrene or silica nanospheres between two treated polycarbonate plates.
  • the nanoparticles were solid spheres, except the 400 nm size, which were hollow:

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